Nitro compounds and process of making same from tar-oils.



UNITED STATES PATENT OFFICE.

com: a. mmnrcx, or NEW YORK, N. Y.

m0 C(SMPOUNDS AND PROCESS OF MAKING SAME FROM TAB-OILS.

Ho Drawing.

To all whom it may concern:

Be it known that I, Jorm R. MARDICK, a citizen of the United States, and residing in New York, county and State of New York, have invented new and useful Improvements in Nitro Compounds and Processes of Making Same from Tar-Oils, of which the following is a specification.

My invention relates to the manufacture of nitro-compounds from distillates of various tars, such for example as coal-tar, watergas t-ar,'and producer-gas tar, or mixtures of such distillates or parts thereof and has for its objects the expeditious production from such materials of relatively large quantities of'nitro-compounds that are highly suitable as waterproofing and stabilizin ingredients for safety explosives, as ingre ients of dynamites to lower the freezing point thereof, as well as serving as substitutes in many cases for tri-nitrotoluene.

I am aware that it has heretofore been proposed to nitrate such a material as solvent naphtha after the removal therefrom of acid and basic components, or of bodies which become resinous with sulfuric acid, such as set forth in Patent No. 898,114 of September 8, 1908. This patent refers to the fact that the nitration of impure tar oil or raw solvent naphtha, while it has been attempted, has heretofore resulted in the production of but a small yield of nitro' solution of soda ash, (1) coal tar distillate having a S. G. from 1.00 to 1.10 (2) impure water-gas tar distillate having a S. G. of 5195 to 1.08; (3)' roducer-gas tar distillate *having a S. G'. o .95 to 1.08; (4) the first two-thirds of the entire distillate of coal tar; (5) the distillate of a tar or mixture of tar distillates having a S. G. between .95 to In carrying out my invention I preferably employ the following special nitration process, as distinguished from the processes customarily employed for nitrating Specification of Letters Patent.

Patented Mar. 5, 1918.

Application filed January 17,1917. Serial a... 142,848.

pure benzol, toluol, etc. In operating for example upon coal tar distillate having a S. G. of 1.00 to 1.10 I employ one and one-half parts of an acid mixture consisting of 45% H NO 38% H 80 and 17% H O, the acid mixture having a S. G. of 1.54 to one part of the aforesaid material, the same being mixed by the gradual addition of the said acid to the oil over a prolon ed period of time, preferably about 7 to 8 ours and the temperature of the nitration bath being maintained by means of constant stirring and coolin during the first two hours between 25 to 30 0., the next three hours between 30 and 35 C. and the last two hours between 35 and 40 C. with the extreme limit preferably 45 C. and in no case above 60 C.

After the nitration has been completed, the acid bath beneath the nitro compounds is withdrawn in the manner customary in the manufacture of tri-rritro-toluene and intro-glycerin and the nitro-compound is vessel with the water maintained at a temperature of about 40 C. The washing operation is preferably repeated about three times. After the washing the nitro-compound obtained, is removed to a kneading machine and washed with several changes of water, about three, or until the water shows no substantial acid reaction. Then a small amount of magnesium carbonate is added to neutralize the acid and the material is thoroughly agitated, whereupon it is again washed with water and any soluble crystalline sa' -s are washed out.

The compound obtained by the aforesaid treatment, which is substantially neutral, is heated until it completely melts, then it is cooled and when cold, if the mixture is stirred in water it will separate out. If desired the same results can be accomplished by means of special centrifugal machines.

The product obtained by nitration in the manner aforesaid of the impure tar distillate or the other raw materials above specified, containing several per cent. of compounds, such as tar acids, tar bases, naphthalene or the like, which are removable by crystallization and repeated washings, not exceeding three, with 2?; to 5% by. weight of cold concentrated sulfuric acid or 5% c ld lution of soda ash, are chara t r ze soluble in benzol, and toluol, substantially.

insoluble in cold water, homogeneously VlS? cons and permanently non-crystalline,

lbrownish in color when isolated, fluid at a temperature in excess of 60 C., substantially soluble in nitro-glycerin when intimately mixed therewith at a temperature of 45 C. and completely miscible with nitroglycerin at normal temperatures. It is preferable that in the production of the herein described products, one-quarter of the total amount of sulfuric acid which is to be employed, should be first slowly added to the distillate prior to the addition of any nitric acid. The-reaction between the sulfuric acid and the tar distillate brings down any resinous bodies as these tend to react with the sulfuric acid in advance of the latter reactin with the tar oil itself. .Accordingly, in view of the small amount of sulfuric acid employed in this preliminary treatment there will be no material action of the nitric acid, when added, upon these resinous bodies until the temperature is raised considerably above 40 0., below which temperature the first stage of the nitration is preferably conducted. Thereby it is possible to more accurately control or regulate the temperature and avoid reaction than if the nitration was conducted by first adding the nitric acid or a mixture of nitric acid and sulfuric acid to the tar distillate operated upon. After the aforesaid preliminary treatment with a portion of the sulfuric acid, the-nitration is-conducted as above described, except that but three-quarters of the total amount of sulfuric acid, as previously set forth herein, is employed in view of the preliminary treatment with sulfuric acid.

The yield of the nitro-compounds obtained in operating for example on coal tar distillate having a S. G. of 1.00 to 1.10 is approximately 125 to 150% of the amount of distillate employed.

The regulation of the temperature control is of the utmost importance in carrying out the manufacture of the herein described products. As neither the tars nor their distillates are good conductors of heat, there .is no substantial distribution of the heat of reaction throughout the mass unless efiective stirring is maintained. Furthermore, since the reaction is rapid and violent in the first stages of the nitration, the temperature unless artificially controlled will soar with the consequence that the products of nitration become gummy or resinous and cling to the sides ofth'e mtrating pot, thus acting as an objectionable insulator to the cooling medium circulating around the pot.

Preferably the air used for cooling is refrigerated to free it from moisture by the well known Gayley process as employed in the steel industry.

Owing to the complexity of the composition of the materials which I employ, it is evident that not only am I able to obtain a high yield of permanently fluent products because of the low melting point of my products owing to the lowermg effect on the melting point of the final product of the numerous nitro-compounds therein, but also my process renders valuable certain materials which would otherwise be suitable for use only after purification, which purification as herein described, results in the elimination in many instances of most desirable products, to saynothingof increasing the melting point of the final products, and even in many instances producing a solid as distinguished from my fluid product, as well as enormouslyreducing the yield. Heretofore,

however, such nitration,- owing to improper control, or for other reasons, has been considered wholly out of the question unless but a portion of the distillate were taken or else a substantial purification of the raw material was first taken. The value of the removable products by purification from the.

raw materials was wholly unappreciated. For the foregoing reasons I disclaim the treatment of any products other than those mentioned in the above classifications and which as set forth therein, contain several per cent. of the compounds removable by crystallization and repeated washings, not .7

quantities of li uid tri-nitro-toluenes, nitronaphthalenes, mtro-benzols, and nitro-zylols, about 2 to 15% by weight'of my improved nitro-compound being preferably employed in conjunction with the other customary ingredients of such plastic powders. Also in the manufacture of black powder, wherein it may be employed as a most efiicient waterproofing and stabilizing ingredient as well as forincreasing the explosive power on explosion, I preferably incorporate 1 to 5% by weight of my improved nitro-prodnot with the other ingredients of such black powder.

While I preferably employ temperatures below 40 C. I do not confine myself to these exact temperatures, and in the claims havecpurposely used the limits of 10 to 60 In produc' the herein described products, if desil i i in lieu of using the mixed acids, the nitric acid can be first added gradually to the materials to be nitrated and then the desired amount of sulfuric acid added separately.

of. It not only serves to waterproof water-- soluble oxidants or oxygen carriers as chlorates, perchlorates, nitrates, permanganates and the like, but also serves to render the same inert to atmosphere in so far as the drying action thereof is concerned, and serves to hold these compounds in their normal condition so that they are not readily exploded by accidental' shocks or affected by atmospheric conditions. V

The term strong nitrating mineral acid includes the class of strong mineral acids commonly used in nitrating organic products, especially either nitric or sulfuric acid.

Thisapplication is a continuation, in part,-

of my copending application No. 101,920, filed June 6, 1916, and patented on the 16th day of October, No. 1,225,347.

Having thus described my invention, what I claim and desire to secure by Letters Patent is 1. The process of preparing permanently semi-liquid, non-volatile, polynitro aromatic-hydrocarbon compounds which consists in first subjecting impure coal-tar, water-gas-tar, or producer-gas tar distillate containing several per cent. of compounds removable by crystallization and repeated washings, not exceeding three, with 2% .to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, to the action of a strong mineral nitrating acid intimately mixed therewith while maintaining the temperature of the mixture below 60 C., and above 10 C., then increasing the strength of said bath by gradually adding a small amount of a strong mineral acid containing nitric acid while still maintaining the temperature of the bath below 60 C.

2. The process of preparing permanently semi-liquid, non-volatile, polynitro compounds, methylated hydrocarbonsfrom impure coal-tar, water-gas-tar, or producer-gas tar distillate containing several per cent. of compounds removable by crystallization by repeated washings, not exceeding three, with 2% to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, which consists in first subjecting the same to the action of astrong mineral nitrating acid gradually added thereto while agitating said mixture and vmaintaining the temperature thereof below 60 C. and above 10 C., then increasing the strength of said bath by gradually adding a small amount of strong nitric acid,

while still maintaining the temperature of the bath below 60 C. I

3. The process of preparing permanently semi-liquid, non-volatile, polynitro compounds, methylated hydrocarbons from impure coal-tar distillate containing several' per cent. of compounds removable by crystallization and repeated washings, not exceeding three, with 2% to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, which consists in first subjecting the same to the action of a strong mineral nitrating acid gradually added thereto while agitating said mixture and maintaining the temperature of the mixture below 60 C.

and above 10 .C., then increasing the strength of said bath by' gradually adding a small amount of a strong mineral acid containing nitric acid, while still maintaining the temperature of the bath below 60 C.

4. The process of preparing permanently semi-liquid, non-volatile, polynitro compounds, methylated hydrocarbons from im-- pure coal-tar distillate of 1.00 to 1.10 S. G. containing several per cent. of compounds removable by crystallizationand repeated washings, not exceeding three, with 2% to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, which consists in first subjecting the same to the action of a strong mineral nitratin acid gradually added thereto while agitating said mixture and maintaining the temperature of the mixture below 60 C. and above 10 C., then increasing the strength of said bath by gradually adding a small amount of a strong mineral acid containing nitric acid, while still maintaining the temperature of the bath below 60 C.

5. The process of preparing permanently semi-liquid, non-volatile, polynitro, aromatic-hydrocarbon compounds which consists in first subjecting impure water-gas tar distillate of .95 to 1.08 S. G., containing several per cent. of compounds removable by crystallization and repeated washings, not exceeding three, with 2;; to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, to the action of a strong mineral nitrating acid intimately mixed therewith while maintaining the temperature of the mixture below 60 C. and above 10 (1., then increasing the strength of said bath by gradually adding a small amount of a strong mineral acid containing nitric acid, while still mail taining the temperature of the bath below 60 C.

6. The process of preparing permanently semi-liquid, non-volatile, polynitro, aroceeding three, with 2% to 5% by weight of concentrated sulfuric acid or solution of soda ash, to the action of a strong mineral nitrating acid intimately mixed therewith while maintaining thetemperature of the mixture below 60 0. and above 0., then increasing the strength of said bath by gradually adding a small amount of a strong mineral acid containing nitric acid, while still maintaining the temperature of the bath below 60 0. v

7. The process of preparing permanently semi-liquid, non-volatile, polynitro, aromatic-hydrocarbon compounds which consists in first subjecting any light portion of either coal-tar or water-gas tar distillate with any portion of heavy distillate'from water-gas tar, containing several per cent. of compounds removable by crystallization and repeated washings, not exceeding three, with 21} to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, to

the action of a strong mineral nitrating acid intimately mixed therewith while maintain- ".ing the tem erature of the mixture below 25 60 0. and a ove 10 0., then increasing the a strength of said bath by gradually adding a small amount of a strong mineral acid containing nitric acid, while maintaining the temperature of the bath below 60 0.

, 8. The olynitro product derived by the nicold water, homogeneously viscous and permanently non-crystalline, of a brownish color, fluid at a temperature in excess of 60 0., substantially soluble in nitro-glycerin when intimately mixed therewith at a temperature of 0., and completely'miscible with nitro-glycerin at normal temperatures.

9. A nitro compound derived by nitration of impure coal-tar distillates of 1.00 to 1.08

S. G. containing several per cent. of compoun s removable by repeated washings, not exceeding three, with 2% to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, such compound being characterized by its partial solubility in hot water, its partial but substantial solubility in benzol and toluol, its substantial insolubility in cold D water, by being homogeneously viscous and permanently non-crystalline, its brownish color, by being fluid at a temperature in ex,- cess of 0., its substantial solubility in nitro-glycerin when intimately mixed therewith at a temperature of 45 0., and its complete miscibility with nitro-glycerin at normal temperatures.

10. A nitro compound derived by nitra-' tion of the first two-thirds of the distillate of coal-tar containing several per cent. of compounds removable by crystallization and repeated washings, not exceeding three, with 2-} to 5% by weight of concentrated sulfuric acid or 5% solution of soda ash, such compound being characterized by its partial solubility in hot water, its partial but substantial solubility in benzol and toluol, by being homogeneously viscous and permanently non-crystalline, its brownish color, by being fluid at a temperature in excess of60 0., its substantial solubility innitroglycerin when intimately mixed therewith at a temperature of 45 0., and its complete miscibility with nitro-glycerin at normal temperatures.

Signed. at New York, county and State of New York, this 15th day of January, 1917.

JOHN R. MARDICK. 

